Production of fuel gases



PRUDUCTIUN 9F FUEL GASES Ernst Bartholom, Heidelberg, Germany, assignorto liodische Anilin- Soda-Fabrilr Ahtiengesellschaft, Ludwigsliafen(Rhine), Germany No Drawing. Continuation of application Serial No.

329,151, December 31., 1952. This application lFebruary as, 1957, SerialNo. 642,367

Qlaims priority, application Germany January 5, 1952 9 Claims. (Cl.48-197) This invention relates to a new and improved method of producingfuel gases, in particular synthesis gases, from gaseous or liquid andcoarse-sized solid fuels.

This application is a continuation of my copending application, SerialNo. 329,151, filed December 31, 1952, and now abandoned.

The conversion of gaseous or liquid hydrocarbons into carbon monoxideand hydrogen by partial oxidation with oxygen in a flame is known to beattended with the formation of carbon black which seriously interfereswith the further processing of the gas produced. By the addition ofsteam or by raising the reaction temperature or increasing the additionof oxygen the formation of carbon black can be diminished, but notcompletely suppressed.

According to the prior art teaching, the formation of carbon black canbe completely suppressed in the conversion of hydrocarbons into carbonmonoxide and hydrogen by partial oxidation by conducting the flamereaction in the presence of small amounts of finely dispersed orvapor-phase compounds of the elements of the second group of theperiodic system and the metals of the iron group. When treated by thismethod the resulting gas, it is true, contains no more carbon black, butthe compounds added may prove a nuisance in the further processing ofthe gas. As a result, this flame reaction cannot be combined in allcases with a subsequent catalytic reaction, for example with a reactionby which the non-converted part of the hydrocarbons reactsendothermically with steam or carbon dioxide while utilizing thesensible heat of the flaming gases, for the reason that the catalyst bedgets clogged by the compounds as the reaction proceeds. When no suchcombination is made, however, the gas needs a high consumption of oxygenfor its production and, as a consequence, the process becomesunsatisfactory under an economical aspect.

I have now found and this is the object of my invention that gaseous andliquid fuels, more specifically hydrocarbon mixtures, can be convertedinto carbon monoxide and hydrogen by partial oxidation with oxygen orgases containing oxygen in the presence of at least one of the aforesaidmetal compounds as a catalyst, with no carbon black being formed, whileutilizing the sensible heat of the off-gases of the flame reaction forthe production of additional carbon monoxide and hydrogen by passing theoff-gases of the flame reaction through a gas producer that operates onthe liquid slag discharging principle and is charged with coarse-sized,solid, carbonaceous fuels, such as coke, mineral coal, briquettes or thelike, arranged in a fixed bed. The foregoing gas producer is alsoreferred to as a slagging gas generator and is described, for example,in Industrial and Engineering Chemistry, 1948, page 559, particularlypage 578. In the gasification of the hydrocarbon, carbon monoxide andhydrogen are substantially formed along with some carbon dioxide andwater. In addition to oxygen or gases containing oxygen endothermicgasifying agents, such as steam and carbon dioxide, may also be used.

hired States Patent 9 The preferred compounds which'may be selected as acatalyst to suppress the formation of carbon black are well known in theart. Suitable catalysts, for example, include compounds of metals of thesecond group of the periodic system and of the iron group. Compoundsfound to be especially useful are, for example, the nitrates, chloridesor hydroxides of magnesium, calcium, strontium, and barium together withnitrates or sulfates of iron, cobalt and nickel.

In the practice of my invention the gaseous or liquid fuels may begasified in a gasification chamber which forms an element of its ownapart from the gas producer, but is attached thereto so that anoperational system exists. In a preferred embodiment it is attached tothe bottom part of the gas producer so that the gases, when leaving theseparate gasification chamber, directly pass into the bottom part of thegas producer.

An alternative embodiment of my invention provides introducing thegaseous or liquid fuels and the gasifying agents directly into thebottom part of the gas producer by means of a burner so that thegasification of the gaseous or liquid fuels is achieved in the gasproducer itself, directly at the burner mouth or near by.

By the process according to my invention the consumption of oxygen forthe carbon monoxide/hydrogen blend produced is cut down to anappreciable extent. Another advantage resides in the fact that the metalcompounds contained in the gases and fed to the flame are removed fromthe gas producer together with the fused ash constituents of the solidfuel. For example, when the gas producer is charged with metallurgicalcoke, a synthesis gas of high purity is obtained which is equal inquality to a synthesis gas which has been produced from metallurgicalcoke in runoff gas producers. When non-caking coal'is used as the chargeof the gas producer, a fuel gas is obtained which is completely free ofcarbon black and of the compounds which have been fed to the flame. Theprocess according to my invention affords the special advantage that bysuitably proportioning the quantities of the gasifying agents and thehydrocarbons, the consumption of coke in the gas producer can be cutdown quite appreciably and, as a consequence, the produced gases, inparticular the synthesis gases, mainly originate from the hydrocarbonsintroduced. The preferred types of hydrocarbons used in the practice ofmy invention-are readily kilograms (per hour) of diesel oil having acontent of 86 percent of carbon and 13 percent of hydrogen and a netcalorific power of 10,000 kilogram-calories for each kilogram aregasified with 97 m. (N. T. P.) (per hour) of oxygen and 40 kilograms(per hour) of steam, which has been previously heated to 500 C., in thepresence of 2 grams (per'hour) of calcium hydroxide and 2.5 grams (perhour) of ferric sulfate, in an atomized state. The hot gases are fedinto a runoff gas producer which is charged with coke. At a gasificationrate of 28.5 kilograms per hour of coke 401 m. (N. T. P.) of a gas areproduced per hour which contains 362 m. (N. T. P.) of carbon monoxideand hydrogen and 39 m. (N. T. P.) of carbon dioxide and water.

Example 2 100 kilograms (per hour) of diesel oil having a content of 86percent of carbon and 13 percent of hydrogen and a net calorific powerof 10,000 kilogram-calories for each kilogram are gasified with 97 111.(N. T. P.)

J (per hour) of oxygen and 40 kilograms (per hour) of steam, which hasbeen previously heated to 500 (1., in the presence of 2 grams (per hour)of calcium nitrate and 0.5 gram (per hour) of nickel nitrate, in anatomized state. The hot gases are fed into a runoff gas producer whichis charged with coke. At a gasification rate of 29.5 kilograms per hourof coke 401 m. (N. T. P.) of a gas are produced per hour which contain362 111. (N. T. P.) of carbon monoxide and hydrogen and 39 111. (N. T.P.) of carbon dioxide and water.

Example 3 100 kilograms (per hour) of diesel oil having a content of 36percent of carbon and 13 percent of hydrogen and a net calorific powerof 10,000 kilogram-calories for each kilogram are gasified with 97 m (N.T. P.) (per hour) of oxygen and 40 kilograms (per hour) of steam, whichhas been previously heated to 500 C., in the presence of 5 grams (perhour) of barium nitrate and 1.0 gram (per hour) of nickel sulfate, in anatomized state. The hot gases are fed into a runoff gas producer whichis charged with coke. At a gasification rate of 29.5 kilograms per hourof coke 401 n1 (N. T. P.) of a gas are produced per hour which contains362 m. (N. T. P.) of carbon monoxide and hydrogen and 39 m. (N. T. P.)of carbon dioxide and water.

The invention is hereby claimed as follows:

1. A process for producing a carbon monoxideand hydrogen-containing fuelgas which comprises: gasifying a fluid hydrocarbon fuel by partialoxidation with an oxygen-containing gas in a flame reaction in thepresence of a dispersed finely divided catalyst to produce principallycarbon monoxide and hydrogen, said catalyst being adapted to suppressthe formation of carbon black; passing the resulting hot gasescontaining said finely divided catalyst through and in contact with asolid carbonaceous fuel arranged in a fixed bed and tindergoinggasification with the formation of liquid slag for the production ofadditional carbon monoxide and hydrogen and for the removal of saidcatalyst from said hot gases; and withdrawing said liquid slagcontaining said catalyst.

2. A process for producing a carbon monoxideand hydrogen-containing fuelgas which comprises: gasifying a fluid hydrocarbon fuel by partialoxidation with an oxygen'containing gas in a flame reaction in thepresence of a dispersed finely divided catalyst to produce principallycarbon monoxide and hydrogen, said catalyst being adapted to suppressthe formation of carbon black in said gasification of said fluidhydrocarbon fuel and said catalyst consisting essentially of at leastone compound of the group consisting of compounds of a metal of the irongroup and compounds of an element of the second group of the periodicsystem; passing the resulting hot gases containing said finely dividedcatalyst through and in contact with a solid carbonaceous fuel arrangedin a fixed bed and undergoing gasification with the formation of liquidslag for the production of additional carbon monoxide and hydrogen andfor the removal of said catalyst from said hot gases; and withdrawingsaid liquid slag containing said catalyst.

3. A process for producing a carbon monoxideand hydrogen-containing fuelgas which comprises: gasifying a fluid hydrocarbon fuel by partialoxidation with oxygen in a flame reaction in the presence of a dispersedfinely divided catalyst to produce principally carbon monoxide andhydrogen, said catalyst being adapted to suppress the formation ofcarbon black in said g:=sification of said fluid hydrocarbon fuel andsaid catalyst consisting essentially of at least one compound of thegroup consisting of compounds of a metal of the iron group and compoundsof an element of the second group of the periodic system; passing theresulting hot git-2cm containing said finely divided catalyst throughand in contact with a solid carbonaceous fuel arranged in a fixed bedand undergoing gasification with the formation of liquid slag for theproduction of additional carbon monoxide and hydrogen and for theremoval of said catalyst from said hot gases; and withdrawing saidliquid slag containing said catalyst.

4. A process as defined in claim 3 wherein the disperscd finely dividedcatalyst adapted to suppress formation of carbon black in saidgasification of said fluid hydrocarbon fuel consists essentially of anitkel compound and a calcium compound.

5. A process for producing a carbon monoxideand hydrogencontainingsynthesis which comprises: gzisifying a fluid hydrocarbon fuel bypartial oxidation with an oxygen-containing gas in a flame reaction inthe presence of a dispersed finely divided catalyst to produ eprincipally carbon monoxide and hydrogen. said catalyst being adapted tosuppress the formation of carbon black in said gasification of saidfluid hydrocarbon fuel and said catalyst consisting essentially of atleast one compound of the group consisting of compounds of a metal ofthe iron group and compounds of an element of the second group of theperiodic system: passing the resulting hot gases containing said finelydivided catalyst through and in contact with coarseized coke arranged inrt fixed bed and undergoing gastfication with the formation of liquidslag for the production of additional carbon monoxide and hydrogen andfor the removal of said catalyst from said hot gases; and withdrawingsaid liquid slag containing said catalyst.

6. A process as defined in claim 1 wherein the said reaction of fluidhydrocarbon fuel is carried out in a aasification Zone. and the said hotgases are introduced into the bottom part of a separate solidcarbonaceous fuel gasification zone.

7. A process as defined in claim 1 wherein the said contacting of solidcarbonaceous fuel with hot gases and gasification of the solidcarbonaceous fuel are carried out in a gasification zone, and the saidgasification of fluid hydrocarbon fuel is carried out in the bottom partof the same zone and in the vicinity of the point of introduction of thefluid hydrocarbon fuel into the zone.

8. A process as defined in claim 1 wherein the consumption of the fluidhydrocarbon fuel is greater than that of the solid carbonaceous fuel.

9. A process as defined in claim 1 wherein the dispersed finely dividedcatalyst adapted to suppress formation of carbon black in saidgasification of id fluid hydrocarbon fuel consists essentially of atleast one compound selected from the group consisting of nitrates andsulfates of iron, cobalt and nickel and nitrates, chlorides andhydroxides of magnesium, calcium, strontium and barium.

References Cited in the file of this patent UNITED STATES PATENTS Hirt cSept. 2-4,

1. A PROCESS FOR PRODUCING A CARBON MONOXIDE- AND HYDROGEN-CONTAININGFUEL GAS WHICH COMPRISES: GASIFYING A FLUID HYDROCARBON FUEL BY PARTIALOXIDATION WITH AN OXYGEN-CONTAINING GAS IN A FLAME REACTION IN THEPRESENCE OF A DISPERSED FINELY DIVIDED CATALYST TO PRODUCE PRINCIPALLYCARBON MONOXIDE AND HYDROGEN, SAID CATALYST BEING ADAPTED TO SUPPRESSTHE FORMATION OF CARBON BLACK; PASSING THE RESULTING HOT GASESCONTAINING SAID FINELY DIVIDED CATALYST THROUGH AND IN CONTACT WITH ASOLID CARBONACEOUS FUEL ARRANGED IN A FIXED BED AND UNDERGOINGGASIFICATION WITH THE FORMATION OF LIQUID SLAG FOR THE PRODUCTION OFADDITIONAL CARBON MONOXIDE AND HYDROGEN AND FOR THE REMOVAL OF SAIDCATALYST FROM SAID HOT GASES; AND WITHDRAWING SAID LIQUID SLAGCONTAINING SAID CATALYST.